Titanium Nitride Hollow Spheres Consisting of TiN Nanosheets and Their Controllable Carbon–Nitrogen Active Sites as Efficient Electrocatalyst for Oxygen Reduction Reaction

Titanium nitride hollow spheres (TiN HSs) consisting of TiN nanosheets have been developed with a carbon-template-assisted strategy. The residual carbon is activated during the removal of the carbon template by calcining at high temperature in the air, and is beneficial for the formation of more carbon–nitrogen active sites. The TiN HSs prepared exhibits a porous and uniform shell with the thickness of ∼30 nm with superior catalytic activity for the oxygen reduction reaction (ORR). The TiN HSs calcined at 325 °C (TiN HSs-325) show the more positive onset potential (0.85 V vs RHE) for ORR and the enhanced limiting current density of up to 4.5 mA cm–2 due to its advantages of unique nanostructure and the controllable active sites. This work provides a promising approach for the design and synthesis of hollow transition metal nitrides with significantly enhanced performances for ORR and other electrochemical energy conversion/storage devices.

[1]  Xiying Li,et al.  Fe–N Co-doped Porous Carbon Derived from Ionic Liquids as an Efficient Electrocatalyst for the Oxygen Reduction Reaction , 2018, Industrial & Engineering Chemistry Research.

[2]  K. Nanda,et al.  CoFe Nanoalloys Encapsulated in N-Doped Graphene Layers as a Pt-Free Multifunctional Robust Catalyst: Elucidating the Role of Co-Alloying and N-Doping , 2018, ACS Sustainable Chemistry & Engineering.

[3]  Taotao Feng,et al.  Co@C Nanoparticle Embedded Hierarchically Porous N-Doped Hollow Carbon for Efficient Oxygen Reduction. , 2018, Chemistry.

[4]  Shan Cheng,et al.  Improved Oxygen Reduction Reaction Performance of Co Confined in Ordered N-Doped Porous Carbon Derived from ZIF-67@PILs , 2017 .

[5]  M. Boujtita,et al.  Titanium vanadium nitride electrode for micro-supercapacitors , 2017 .

[6]  Jun Liu,et al.  A facile route to graphite-tungsten nitride and graphite-molybdenum nitride nanocomposites and their ORR performances , 2016 .

[7]  R. Behm,et al.  Spherical Core–Shell Titanium (Oxy)nitride@Nitrided Carbon Composites as Catalysts for the Oxygen Reduction Reaction: Synthesis and Electrocatalytic Performance , 2016 .

[8]  B. Lei,et al.  Engineering Multimetallic Nanocrystals for Highly Efficient Oxygen Reduction Catalysts , 2016 .

[9]  S. Liao,et al.  Limitations and Improvement Strategies for Early-Transition-Metal Nitrides as Competitive Catalysts toward the Oxygen Reduction Reaction , 2016 .

[10]  N. Kim,et al.  Facile synthesis of vanadium nitride/nitrogen-doped graphene composite as stable high performance anode materials for supercapacitors , 2016 .

[11]  Liangti Qu,et al.  N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions. , 2016, Angewandte Chemie.

[12]  H. Fu,et al.  Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions , 2016, Nano Research.

[13]  Wei Li,et al.  Cobalt modified two-dimensional polypyrrole synthesized in a flat nanoreactor for the catalysis of oxygen reduction , 2015 .

[14]  N. Zhang,et al.  Nitrogen-Doped Carbon Nanotube Aerogels for High-Performance ORR Catalysts. , 2015, Small.

[15]  Wei Chen,et al.  Graphene-supported nanoelectrocatalysts for fuel cells: synthesis, properties, and applications. , 2014, Chemical reviews.

[16]  Teng Zhai,et al.  Improving the Cycling Stability of Metal–Nitride Supercapacitor Electrodes with a Thin Carbon Shell , 2014, Advanced Energy Materials.

[17]  Jinghong Li,et al.  Titanium nitride nanocrystals on nitrogen-doped graphene as an efficient electrocatalyst for oxygen reduction reaction. , 2013, Chemistry.

[18]  K. Müllen,et al.  Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction. , 2013, Journal of the American Chemical Society.

[19]  Jinghong Li,et al.  Electrocatalysis on shape-controlled titanium nitride nanocrystals for the oxygen reduction reaction. , 2013, ChemSusChem.

[20]  Haoshen Zhou,et al.  Carbon supported TiN nanoparticles: an efficient bifunctional catalyst for non-aqueous Li-O2 batteries. , 2013, Chemical communications.

[21]  S. Didziulis,et al.  A perspective on the properties and surface reactivities of carbides and nitrides of titanium and vanadium , 2013 .

[22]  Yao Zheng,et al.  Nanostructured metal-free electrochemical catalysts for highly efficient oxygen reduction. , 2012, Small.

[23]  Yang‐Kook Sun,et al.  Fine control of titania deposition to prepare C@TiO2 composites and TiO2 hollow particles for photocatalysis and lithium-ion battery applications , 2012 .

[24]  P. He,et al.  Nano- and micro-sized TiN as the electrocatalysts for ORR in Li–air fuel cell with alkaline aqueous electrolyte , 2012 .

[25]  Y. Qian,et al.  Synthesis of TiN hollow sphere by a modified one-step template self-assembly method , 2012 .

[26]  D. Mitlin,et al.  High Rate Electrochemical Capacitors from Three-Dimensional Arrays of Vanadium Nitride Functionalized Carbon Nanotubes , 2011 .

[27]  Yan-Jie Wang,et al.  Noncarbon support materials for polymer electrolyte membrane fuel cell electrocatalysts. , 2011, Chemical reviews.

[28]  M. Antonietti,et al.  Nano-sized TiN on carbon black as an efficient electrocatalyst for the oxygen reduction reaction prepared using an mpg-C3N4 template. , 2010, Chemical communications.

[29]  Yadong Li,et al.  Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles. , 2004, Angewandte Chemie.

[30]  Jingguang G. Chen Carbide and Nitride Overlayers on Early Transition Metal Surfaces: Preparation, Characterization, and Reactivities. , 1996, Chemical Reviews.